Oil-soluble metal-containing materials and methods for preparing same



United States Patent OIL-SOLUBLE METAL-CONTAINING MATERIALS AND METHODS FOR PREPARING SAME No Drawing. Application February 15, 1954, Serial No. 410,437

Claims. (Cl. 25242.7)

This invention relates as indicated to oil-soluble metalcontaining materials and more particularly to a novel composition of matter which contains unexpectedly large amounts of barium in oil-soluble form.

The use of barium compounds in lubricating compositions has become quite wide-spread in recent years, these compounds being principally of the class known as detergents. Such detergents which contain barium have been found to be more generally applicable to the problems of motor lubrication than those detergents which contain other metals. Furthermore, the amount of barium which is present in these detergents has been found to be significant; i. e., the more barium which is present in oilsoluble form the more effective is the compound with respect to its detergent qualities.

The methods by which a metal may be incorporated into an oil solution have heretofore been limited to the utilization of the metal salts of acidic materials. Until recently only those metal salts which are oil-soluble were used. Such salts are limited as to the proportion of metal which they can assimilate in oil-soluble form, this upper limit being about 2.2 times the amount of metal which is present in the normal salt. More recently, methods have been found whereby normally oil-insoluble metal salts may be employed and by virtue of these methods much higher proportions of metal can be incorporated into oilsoluble complexes. Thus, for example, it has been learned that such oil-insoluble salts as magnesium methylate, barium phenate, barium salt of l-nitropropane, etc. can be used very effectively to promote the incorporation of large amounts of metal into oil-soluble complexes. These and all other previously known oil-soluble complexes necessarily contain, in addition to the normally oil-insoluble metal salt, an oil-soluble salt such as calcium petroleum sulfonate, barium petrolatum sulfonate, strontium naphthenate, barium dihexyldithiophosphate, magnesium petroleum sulfonate, etc.

It will be seen from the foregoing that methods of incorporating metal into oil-soluble compounds or complexes have heretofore depended on the utilization of salts of acidic materials, usually sulfonates. Whether these previously known complexes are true chemical complex compounds whose formation depends upon the promoting action of such acidic compounds or whether the complexes are merely colloidal suspensions which depend upon the salts of acidic compounds as dispersing or peptizing agents, the presence of these salts has been deemed essential.

It is accordingly an object of this invention to provide a novel method of incorporating metal into oil-soluble materials. It is a further object to provide such a method which is independent of the presence of acidic materials. It is still a further object to provide new compositions of matter for use in lubricating oils.

Other objects of the invention will appear as the description proceeds.

To the accomplishment of the foregoing and related ends, said invention then comprises the features herein- Patented July 9, 1957 neutral hydrocarbon oxidation product. The method by which this may be accomplished comprises heating a mixture of metallic base, such as a metal oxide or hydroxide, and a petroleum hydrocarbon fraction containing a hydrocarbon oxidation product. The presence of acidic products is not essential to the successful operation of this method.

Broadly stated, this invention relates to a method of preparing oil-soluble metal-containing materials which comprises heating a mixture containing at least one oilsoluble ketone, at least one alcohol, and metallic base.

More particularly, this invention relates to a process for the preparation of oil-soluble liquid, filtrable compositions containing large amounts of metal which comprises: preparing and mixing a mass in which at 50 C., at least 50% of the mass is in the liquid state, and in which mass the active components consist essentially of:

(A) at least one oil-soluble non-volatile ketone having a hydrocarbon residue of at least 13 carbon atoms and a boiling point above 225 C.;

(B) at least one hydroxy organic compound of the formula:

wherein Q is a substituted or unsubstituted cyclic or acyclic organic radical; n is an integer from one to four, and OH is bonded to a non-benzenoid carbon atom in Q; said hydroxy organic compound having an ionization constant not greater than l 10- in water at 25 C.;

(C) at least one metal base having a pH greater than 7 in aqueous solutions at 25 C.;

heating the mass at a temperature and for a period of time sufficient to form the oil-soluble complex material; and optionally, treating the mass with a Weak inorganic acidic material having an ionization constant within the range from about l l0 to 1X10 in aqueous solutions at 25 C., i. e. values higher than the ionization constant of said hydroxy organic compound of component (B), in amounts suflicient to substantially reduce the basicity of the mass.

COMPONENT ATHE OIL-SOLUBLE KETONES The ketones may also be obtained from oxidized petroleum fractions; such fractions may contain hydrocar-j bons which are saturated or unsaturated, straight or branched chain, solid or liquid, aromatic aliphatic (paraffinic) or cycloaliphatic (naphthenic). All of the above,

either singly or in admixture with one another, have been. found to be operative in the process ofthis invention.

More specific examples of petroleum fractions which will be used in the practice of this invention include eicosane, petrolatum, white oil, a highly unsaturated wax, a phenol-extracted aromatic fraction, scale wax;

solvent-extracted mid-continent oils, etc. A cursory in spection of these petroleum latum as an example of a slightly unsaturated, branchedchain material; white oil as an example of a mixture of saturated-chain and branched-chain materials. The highly unsaturated wax Was prepared by chlorination of a wax fraction, followed by dehydrochlorination, yielding a product with a bromine number in the range of about 60-75. The phenol-extracted aromatic fraction contains about percent of aromatic compounds, 30 percent of naphthenic compounds, and 50 percent of parafiinic compounds. Scale wax is an example of a mixed straight and branched-chain material.

The method for forming the ketone starting materials by the oxidation of these petroleum fractions is not critical. A wide variety of oxidation methods is known and any of these may be employed. It has been found, for example, that such a simple method as allowing a sample of a petroleum fraction to be exposed to atmospheric oxygen at room temperature for a prolonged period of time gives an entirely satisfactory material for the preparation of products of this invention. It will usually be desirable to utilize oxidation processes which require less time. Such processes involve higher temperatures and at such temperatures catalysts may be employed. Thus, it has been observed that petroleum fractions may be oxidized satisfactorily at about 200 C. at a period of 4 to 12 hours. The use of oxidation catalysts allows an even shorter time.

The oxidation product may itself be utilized directly to prepare the oil-soluble metal-containing complex materials, provided it contains sutlicient ketones, and provided that the carboxylic acid content and ester content of the oxidation product are not very high. A relatively high carboxylic acid and ester content in the oxidation product gives rise to a metal-containing material which is a solid grease-like, unfilterable substance. Furthermore, such a material is not soluble in mineral lubricating oils, and so is of considerably reduced value as an improving agent for fluid lubricants. For these reasons, it is preferred to use as a starting material an oxidized hydrocarbon which is substantially free from carboxylic acids and their esters. Such starting materials may be fractions reveals eicosane as an example of a saturated straight chain compound, petro obtained either by oxidizing a hydrocarbon incompletely under mild conditions, or by oxidizing a hydrocarbon under more strenuous conditions and subsequently removing the carboxylic acids and esters of saponificatiou and aqueous extraction. The oil-soluble ketone formed by the oxidation of the petroleum fraction must be present for the preparation of oil-soluble metal-containing materials, although minor amounts of other oxidation products may be present without hampering the process described herein.

Of the various types of oil-soluble ketones, enumerated above, it is preferred to employ the ketones obtained by the oxidation of petroleum hydrocarbon fractions because of their cheapness and ready availability.

COMPONENT BORGANIC HYDROXY COM- POUND STARTING MATERIALS The broad class of compounds useful as this reagent may be represented by the formula wherein Q is a substituted or unsubstituted cyclic or acyclic organic radical having at least one non-benzenoid carbon atom; n is an integer of from 1 to 4, preferably 1 to 3, and most desirably 1; and OH is bonded to a nonbenzenoid carbon atom in Q; said compound Q(OH)7L having an ionization constant not greater than l 10 in water at 25 C. Y

The above formula includes, as its most numerous class, the various monohydric and polyhydric alcohols, of which the monohydric alcohols are preferred. While excellent results are obtained, as shown hereinafter, with unsubstituted monohydric alcohols; i. e., alcohols containing only carbon, hydrogen, and hydroxyl oxygen, for some purposes, as, for example, use of the end-products of the invention in lubricants, it is often desirable to employ an alcohol which contains at least one substituent group such as; e. g. halogen, amino, sulfide, disulfide, ether, etc.

Bests results are usually obtained With monohydric alcohols which do not contain a homocyclic benzenoid ring structure and which have a molecular weight less than 150.

Illustrative of the various Q(OH)11. compounds which may be used in accordance with the invention are: unsubstituted aliphatic monohydric alcohols; e. g., methyl, ethyl, propyl, isopropyl, butyl-sec-butyl, isobutyl, tertiarybutyl, amyl, n-hexyl, 4-methyl-pentyl-2, heptyl, n-octyl, capryl, n-nonyl, isononyl, 2-ethyl-hexyl, decyl, lauryl, and tetradecyl alcohols; substituted aliphatic monohydric alcohols; e. g. chloro-hexyl, bromo-octyl, fluoro-decyl, amino-ethyl, methoxyethoxyethyl, and methylmercaptoethyl alcohols; substituted cycloaliphatic monohydric alcohols; e. g. cyclohexyl, methyl-cyclohexyl, propyl-cyclohexyl, amyl-cyclohexyl, octyl-cyclohexyl, tetrahydrofurfuryl, and decahydronaphthyl alcohols; substituted cycloaliphatic monohydric alcohols; e. g. 2-chloro-cyclohexyl and chlorinated methyl-cyclohexyl alcohols; aromatic-substituted aliphatic monohydric alcohols; e. g. benzyl, pch'lorobenzyl, p-aminobenzyl, phenethyl, p-chlorophenethyl, and furfuryl alcohols; cycloaliphatic-substituted aliphatic monohydric alcohols; e. g., cyclohexyl-methyl, cyclohexyl-ethyl, and methyl-cyclohexyl-ethyl alcohols; and the various polyhydric alcohols which contain from 2 to 5 hydroxyl groups; e. g., ethylene glycol, propylene glycol, butylene-glycol, glycerol, cyclohexandiol-1,4, pentaerythritol, and the like.

It is also within the scope of the present invention to use mixtures of two or more Q(OH)n compounds. Particularly useful in some instances are combinations of a low-boiling alcohol, such as methanol, with a high-boiling alcohol, such as isononyl alcohol.

L COMPONENT CBASE METAL COMPOUNDS Metal oxides and hydroxides comprise the principal and most useful constituents of this group; others are the sulfides, hydrosulfides, alcoholates, etc. Specific examples of the more useful basic metal compounds include barium oxide, barium hydroxide, lithium oxide, lithium hydroxide, barium alcoholates, etc. Good results are obtained with basic metal compounds having a pH value greater than 7 in water at 25 C.

THE INORGANIC Acrmc MATERIAL As previously indicated, one form of the process of the present invention includes the step of treating the immediate complex material with a weak inorganic acidic material for the purpose of reducing the basicity of the mass. The effective inorganic acidic materials have ionization constants within the range from about 1 l0- to about 1 l0- in aqueous solutions at 25 C., i. e., values higher than the ionization constant of the organic hydroxy compounds of component B.

It is to be understood that the acidic material can be either a liquid, gas, or solid, prior to being incorporated into the mass. However, the acidic material is usually a gas or a liquid. The liquids include, for example, the weak inorganic acids such as carbonic, nitrous, chromic acids, etc., whereas the gas for the most part is an anhydride of an acid, or an acid anhydride gas. The following are additional specific examples of acidic materials, viz.: CO2, air (considered acidic because of CO2 content), N02, H28, CS2, etc.

It is to be understood, however, that all acidic materials are not equivalent for the purposes of the present invention, but that under certain conditions some are more effective or desirable than others. Carbon dioxide has been found to be a particularly effective acidic material.

A substantial amount of the acidic material is usually employed in the process, generally to substantially reduce the titratable basicity of the mass, and usually in amounts sufficient to substantially neutralize the mass.

PROCESS CONDITIONS The oil-soluble metal-containing materials of this invention may be prepared by mixing the oil-soluble ketone, or its oil-soluble metal salt, with a Q(OH)11. compound, and a basic metal compound and heating the mass at a temperature and for a period of time sufficient to form the oil-soluble metal-containing complex material.

The amount of organic hydroxy compound which is to be employed as component B in the process is not critical, and it is necessary only that an appreciable amount be used Thus, for each equivalent weight of basic metal compound which is used at least 0.1 equivalent weight of organic hydroxy compound will usually be employed. Preferably the amount of organic hydroxy compound will be 0.25 equivalent or more on the same basis.

The amount of metal base employed in the process is usually substantially greater than the equivalent amount of oil-soluble ketone. In other words, the amount of metal base employed should be such that there is more than the theoretical amount required to form merely the normal salt of the oil-soluble ketone. Thus, the amount of metal base employed will be expressed as an amount such that there is present in the mass more than one equivalent of metal, including the metal present in the form of the salt of the oil-soluble ketone, per equivalent of oil-soluble ketone and metal salt thereof.

The method of incorporating metal into the oil-soluble materials of this invention merely comprises heating a mixture comprising oil-soluble ketones, organic hydroxy compounds, and metal base. The mixture may be heated at an elevated temperature for a substantial period of time, for example, one hour at reflux temperature. After this time, the temperature may be raised and the organic hydroxy compound distilled off and the heating continued at elevated temperatures within the range from about 150 C. to 300 C. and higher. There is no apparent upper limit to the reaction temperature as long as the temperature is not so high as to cause substantial decomposition of the organic reactants. Appreciable quantities of metal may be incorporated into the mass at temperatures at 150 C., although the time required for such a reaction at this temperature is quite long, and according 1y it is preferred to carry out the process at higher temperatures, preferably in the range from about 280 C. to 320 C.

The process may be carried out either in an inert at mosphere, such as nitrogen, or it may be carried out in the presence of oxygen in the atmosphere. Either set of conditions yields a satisfactory product.

The oil-soluble metal-containing complex materials may have a substantial titratable alkalinity. If a neutral oilsoluble metal-containing product is desired, it is neces sary only to treat the alkaline product with a Weakly acidic material, such as carbon dioxide, carbon disulfide, 11y drogen sulfide, etc. If a strongly acidic material is utilized, the resulting product contains little or no metal.

The invention may beillustrated in greater detail by the examples which are presented hereinafter solely for purposes of illustration, and not as limitations on the invention.

Example 1 (.A) A 6500 gramvsample of eicosane was stirred at 200 C. whilela .stream of air was bubbled through at a rate of one liter per minute for 14 hours. The product was mixed with 400 grams of potassium hydroxide and 4000 cc. of. ethyl alcohol and heated at reflux temperature for four hours. This mixture was cooled and Washed five times with hot water, then dried at 180 C./ 20 mm.

The product weighed 5424 grams and showed the following analysest.

Percent hydroxyl Percent carbonyl 1.3 Acid number 0.66 Saponification number 1.0

A mixture of 166 grams of barium oxide, 250 cc. of methanol and 500 grams of a saponified oxidation product prepared as indicated in Example 1 Was heated at reflux temperature for one hour. The methanol was. removed and the temperature was raised to SOD-320 C. and held there for three hours. The cooled mixture was treated with Hyflo and filtered. The filtrate was oilsoluble, weighed 578 grams and showed a barium sulfate ash value of 34.8 percent.

Example 3 A 500 gram sample of eicosane was stirred at 195-205 C. while air was blown through ata rate of one liter per minute for 13.5 hours, then allowed to cool. The oxidized product weighed 4700 grams and showed the following analyses:

Percent hydroxyl 0.57 Percent carbonyl 2.0 Acid number 7.2 Saponification number 26.0

This oxidation product was treated with 2000 cc. of ethyl alcohol and 311 grams of potassium hydroxide and the whole was stirred at reflux temperature for four hours. The cooled product mixture was washed five times with water, than dried at 160 C./25 mm. The yield of product was 4071 grams, and its analyses were:

Percent hydroxyl 0.84 Percent carbonyl 1.45 Acid number 0.44 Saponification number 1.14

The above saponified product was stirred with 1660 cc. of methanol and 1092 grams of barium oxide at reflux temperature for one hour. The methanol was removed by distillation and the temperature was raised to 295- 310 C. where it was maintained for four hours. The product mixture was allowed to cool, then treated with I-Iyflo and filtered. The filtrate was oil-soluble, weighed 4228 grams and showed a barium sulfate ash value of 30.6 percent.

Example 4 A 3205 gram sample of refined mid-continent oil was treated with a stream of air (one liter per minute) at -210 C. for 13.5 hours. Theproduct weighed 3194 grams and showed the following 'analysesi Percent hydroxyl Q. Nil Percent carbonyl 2.1 Acid number 2.6

Saponification number 14.0

"7 Percent hydroxyl 0.12 Percent carbonyl 0.5 Acid number Trace Saponification number Nil Example A 1438 gram sample of white oil was stirred at 200 C. while air was bubbled through for seven hours at a rate of one liter per minute. The product weighed 1432 grams and showed the following analyses:

Percent hydroxyl Nil Percent carbonyl 0.5 Acid number 0.5 Saponification number 4.6

This oxidation product was mixed with 92 grams of potassium hydroxide and 920cc. of ethyl alcohol and heated at reflux temperature for four hours. The product was washed five times with hot water, then dried at 150 C./ 14 mm. The residue weighed 1262 grams and showed the following analyses:

Percent hydroxyl Trace Percent carbonyl 0.3 Acid number Trace Saponification number 0.6

This saponification product was mixed with 260 grams of barium oxide and 405 cc. of methanol and heated at reflux temperature for one hour. The methanol was removed by distillation and the temperature was raised to 300 C. where it was maintained for four hours. The product was allowed to cool, then was treated with Hyflo and filtered. The filtrate was oil-soluble, weighed 860 grams and showed a barium sulfate ash value of 4.7 percent.

Example 6 A 1500 gram sample of white oil was stirred at 200 C. while a stream of air was bubbled through for 6.5 hours. The product weighed 1493 grams and showed the following analyses:

Percent hydroxyl Trace Percent carbonyl 2.0 Acid number 1.6 Saponification number 10.6

This oxidation product was mixed with 95 grams of potassium hydroxide and 950 cc. of ethyl alcohol and heated at reflux temperature for four hours. The product was washed five times with hot water, then dried at 150 C./20 mm. The residue weighed 1305 grams and showed the following properties:

Percent hydroxyl 0.2 Percent carbonyl 0.6 Acid number Trace Saponification number 0.7

This material was treated with 269 grams of barium oxide and 410 cc. of methanol and the whole was heated at reflux temperature for one hour. The methanol was removed by distillation and the temperature was raised to 300 C. and held there for four hours. The product mixture was allowed to cool, then treated with Hyflo and filtered. The filtrate was oil-soluble, weighed 938 grams and had a barium sulfate ash value of 9.0 percent.

8 Example 7 p A 1400 gram sample of a solvent-refined Mid-Continent oil was stirred at 200 C. while a stream of air was bubbled through at one liter per minute for six hours. The product weighed 1395 grams and showed the following analyses:

Percent hydroxyl Nil Percent carbonyl 4.1 Acid number 1.4 Saponification number 0.13

This oxidation product was mixed with grams of potassium hydroxide and 900 cc. of ethyl alcohol and heated at reflux temperature for four hours. The product mixture was washed five times with hot water then dried at 153 C./ 13 mm. The residue weighed 1230 grams and showed the following analyses:

Percent hydroxyl Trace Percent carbonyl 0.5 Acid number Nil Saponification number Nil The residue was mixed with 252 grams of barium oxide and 400 cc. of methanol and then heated at reflux temperature for one hour. The methanol was removed by distillation and the temperature then raised to 300 C. and held there for four hours. The mixture was allowed to cool, then was treated with Hyflo and filtered. The filtrate was oil-soluble, weighed 780 grams and had a barium sulfate ash value of 5.1 percent.

Example 8 The oil-soluble barium-containing material prepared as indicated in Example 3 was concentrated by heating at 188 C./ 1.2-2.0 mm. until 223 grams of a white, waxy distillate was obtained. The residue was filtered yielding an oil-soluble filtrate which had a barium sulfate ash value of 67.6 percent and a basic number of 57.3. The distillate showed the following analyses:

Percent hydroxyl Trace Percent carbonyl 0.3 Acid number Trace Saponification number 0.3

.The following Example 9 illustrates the process employing a ketone, other than those obtained by the oxidation of petroleum hydrocarbon fractions.

Example 9 A mixture of grams of stearone, 180 grams of eicosane, 73 grams of barium oxide and cc. of methanol was heated at reflux temperature in an atmosphere of nitrogen for one hour. The methanol was removed by distillation and the temperature was raised to 295-310 C. where it was maintained for four hours. The mixture was cooled, treated with a siliceous filter aid and filtered. The filtrate was oil-soluble, weighed 310 grams and had a barium sulfate ash value of 20.6 percent.

The following examples, 10 through 13, show how the basicity of the mass may be reduced by treatment with weakly acidic inorganic material.

Example 10 (A) A mixture of 500 grams of unsaturated wax which had been oxidized by prolonged exposure to air at room temperature, 166.5 grams of barium oxide and 500 cc; of methanol was heated in an atmosphere of nitrogen at reflux temperature for one hour. The methanol was removed by distillation and the temperature was raised to 300 C. and held there for four hours. The mixture was allowed to cool, then was treated with Hyflo and filtered. The filtrate was oil-soluble, weighed 482 grams and had a barium sulfate ash value of 23.4 percent and a basic number of 38.4.

(B) A 200 gram sample of oil-soluble. barium-com taining material prepared as indicatedabove, and having a barium sulfate ash value of 23.0 percent and a basic number of 38.4 was treated with 50 grams of hydrogen sulfide bubbled into the liquid. "The temperature of the mass was raised gradually. from 30 C. to 205 C. at which latter temperature it was held finally for one hour. The cooled mixture was treated with Hyfl'o and filtered. The filtrate was oil-soluble, weighed 124 gramsand had a barium sulfate ash value of 22.8 percent, a sulfuricontent of 2.08 percent and a basic number of 7.9.

Example 11 A 200 gram sample of oil-soluble barium-containing material as prepared above in Example (A), having a barium sulfate ash value of 23.0 percent and a basic number of 38.4, was mixed with 90 grams of carbon disulfide and heated at reflux temperature for one hour. The carbon disulfide then was removed by evaporation. The residue was treated with Hyfio and filtered. The filtrate was oil-soluble, Weighed 191 grams and had a barium sulfate ash value of 22.4 percent, a sulfur content of 1.91 percent, and a basic number of 9.7.

Example 12 A 5855 gram sample of eicosanewas heated at 180- 190 C. while air was bubbled through for 12.5 hours. This duct was treated with 2300 grams of alcohol and then while stirring 225 grams of potassium hydroxide was added. When the potassium hydroxide had dissolved the resulting mixture was heated for four hours at reflux temperature. This product was. treated withnaphtha, and then washed four times with an equal volume of water. The washed product was evaporated to afinal temperature of 180 C. at 35 mm.

(A) 1702 grams of the above product was treated with 465 grams of barium oxide and 850 ml. of methanol This mixture was heated at reflux temperature for one hour in an atmosphere of nitrogen and then the methanol was removed by evaporation. The residue was heated for three hours at 295 to 310 C. The resulting prod uct was filtered through Hyflo.

(B) The product of (A) above was heated to 200 C. at which temperature carbon dioxide was bubbled in for two hours. The product showed the following analyses:

Sulfate ash 33.8% Neut. No 0.39 (acidic) (C) To 510 grams of the product obtained from (A) above there was added 120 grams of carbon disulfide, and this mixture was heated at reflux temperature for three hours. Carbon disulfide was removed by heating to a final temperature of 80 to 120 C. at 55 mm. The residue was filtered through Hyflo to yield a filtrate having the following analyses:

Sulfate ash 25.1% Neut. No 3.8 (basic) Example 13 A mixture of 325 grams of stearone, 197 grams of barium oxide, 300 ml. of methanol, and 100 ml. of toluene was heated at reflux temperature for one hour. The volatile materials were removed by distillation and the residue was heated for an additional four hours with stirring at 295 to 310 C. This product was cooled and treated with a mixture of carbon dioxide and nitrogen for two hours at 160 to 200 C. The resultant product was treated with 350 grams of mineral oil and then filtered through Hyflo. The filtrate had the following analyses:

Sulfate ash 30.0% Neut. No 2.88 (acidic) It will be noted in Examples 10, 11, 12 and 13 above, that while the basicity of the product is substantially reduced, the barium content is essentially unchanged.

In Examples 14, 15 and 16 below, the product. was treated with a strongly acidic inorganic mate-rial outside of the ionization constant specified for such acidic material. -It' will be seen that the metal content of the prod not was substantially reduced using strongly acidic inorganic materials.

Example 14 (A) A sample: of unsaturated petroleum wax which had been oxidized by prolonged exposure to air at room temperature and which weighed 2500 grams was treated with 834 grams of barium oxide and 1500 cc. of methanol. This mixture was stirred in an atmosphere of nitrogen at reflux temperature for two hours, at which point the methanol was removed by distillation and the temperature was raised to 305 C. and held there for four hours. The product mixture was allowed to cool, then was treated with Hyflo and filtered. The filtrate was oil-soluble, weighed 2360 grams (71. percent) and showed a barium sulfate ash value of 21.8 percent and a basic number of 35.4. p

(B) A 150 gram sample of oil-soluble barium-containing material prepared as indicated above and having a barium sulfate ash value of 23.0 percent and a basic number of 38.4 was treated with 40 grams of sulfur dioxide gas bubbled into. the liquid at room temperature. An exothermic reaction ensued and a thick viscous mass resulted. It was diluted with500 cc. of benzene and filtered and the filtrate'wa-s freed of benzene by distillation. The residue showeda negligible barium sulfate ash value of 0.23 percent.

Example 15 A mixture of 200 grarns -of oil-soluble barium-containing material prepared as indicated in Example 10 (A), 300 cc. of benzene, cc. of concentrated hydrochloric acid and 500 cc. of water was heated for three hours at 50-70 C. The organiclayer was isolated and washed, twice with warm water. It was dried at 100 C./ 25 mm., then filtered. The filtrate showed a negligible barium sulfate ash value of 0.84 percent.

Example 16 A mixture of grams of the oil-soluble product ob-, tained as described in Example 9, 200 cc. of benzene, 150 cc. of concentrated hydrochloric acid and 500 cc. of water was heated at reflux temperature for two hours. The organic layer was isolated and washed three times, with warm water, then dried at C./ 50 mm. The residue was filtered yielding a filtrate which had a barium sulfate ash value of 0.07.

- Example 17 280 grams (0.5 5 mole) of laurone, 200 ml. of methanol, and 200 ml. of toluene was stirred in a flask under an atmosphere of nitrogen while grams (1.11 moles) of BaO were added. After all the BaO has been added, the whole was refluxed for one hour. Thereafter, the reflux condenser was changed to the distilling position and the mixture was heated slowly to 275 C., while maintaining an atmosphere of nitrogen in the flask and removing the methanol and toluene solvents.

The whole was then heated at 275-300 C. for 3 hours in the nitrogen atmosphere. Filtration of the reaction mass yielded 370 grams of a viscous, oil-soluble, brownred, liquid barium complex having the following analyses:

Percent sulfate ash 43.7 Basic No 62.5

Example 18 288 grams (0.73 mole) of Coconone (a high molecular weight aliphatic ketone of undetermined composition available from the Vegetable Oil Products Company), 300 ml. of methanol, 200 ml. of toluene, and 224 grams (1.46 moles) of BaO were reacted together in the manner set forth in Example 17.

11 Filtration of the reaction mass yielded 240 grams of a brown, oil-soluble, liquid barium complex having the following analyses:

Percent sulfate ash Basic No Example 19 A mixture of 420 grams of laurone, 253 grams of barium oxide, 100 ml. of toluene and 161.5 grams of furfuryl alcohol was stirred'at 90110 C. for 30 minutes, then at 160 C. for four hours, and finally at 270-290 C. for four hours. The hot mixture was filtered through Hyfio; the filtrate was a reddish-brown, slightly viscous liquid having the following analyses:

Percent sulfate ash 46.3 Neut. No 24 (basic) Example Percent sulfate ash 24.5 Neut.No 27.2 (basic) Other modes of applying the principle of the invention may be employed, change being made as regards the details described, provided the features stated in any of the following claims, or the equivalent of such, be employed. We therefore particularly point out and distinctly claim as our invention:

1. A process for the preparation of oil-soluble liquid, filterable compositions containing large amounts of metal which comprises: preparing and mixing a mass in which at 50 C., at least 50% of the mass is in the liquid state, and in which mass the active components consist essentially of at least one each of each of the following components: (a) a substantially neutral, aliphatic ketone having at least 13 carbon atoms and a vapor pressure less than atmospheric at 225 C.; (b) a monohydric alcohol containing no homocyclic benzenoid ring and having a molecular weightless than 150; (c) a basically reacting inorganic metal compound having a pH greater than 7 in aqueous solutions at 25 C. in an amount equal to at least 1.5 times the amount of (a) on an equivalence basis; heating the mass to a temperature of from about 250 C. to about 350 C. for a period of at least about 1 hour.

2. A process for the preparation of oil-soluble liquid,

filterable compositions containing large amounts of alkaline earth metal which comprises: preparing and mixing a mass in which at 50 C., at least 50% of the mass is in the liquid state, and in which mass the active components consist essentially of at least one each of each of the following components: (a) a substantially neutral, aliphatic ketone having at least 13 carbon atoms and a vapor pressure less than atmospheric at 225 C.; (b) a monohydric aliphatic alcohol containing no homocyclic benzenoid ring and having a molecular weight of not more than about (c) a basically reacting inorganic alkaline earth metal compound having a pH greater than 7 in aqueous solutions at 25 C. in an amount equal to at least 1.5 times the amount of (a) on an equivalents basis; heating the mass to a temperature of from about 250 C. to about 350 C. for at least about 1 hour.

3. A process for the preparation of oil-soluble bariumcontaining compositions which comprises admixing (a) a substantially neutral, aliphatic ketone having at least 13 carbon atoms and a vapor pressure less than atmospheric at 225 C.; (b) an alcohol containing no homocyclic benzenoid ring and having a molecular weight of not more than about 150 in an amount equal to at least 1.5 times the amount of (a) on an equivalence basis; and (c) an inorganic barium-oxy base; then heating said admixture to 250350 C. for at least about two hours.

4. The process of claim 1 further characterized by the step of treating the mass with a weak inorganic acidic material having an ionization constant within the range from about 1X10- to 1 10- in aqueous solutions at 25 C., and higher than the ionization constant of said aliphatic alcohol of component (b), in amounts suiiicient to substantially reduce the basicity of the mass.

5. The process of claim 1 further characterized in that said ketone is an oxidized petroleum fraction.

6. The process of claim 1 further characterized in that said ketone is laurone.

7. The process of claim 1 further characterized in that said ketone is stearone.

8. The process of claim 1 further characterized in that said ketone is coconone.

9. The process of claim 2 further characterized in that said alcohol is an alkyl alcohol.

10. The process of claim 2 further characterized in that said alcohol is methanol.

References Cited in the file of this patent UNITED STATES PATENTS 2,487,840 Van Ess Nov. 15, 1949 2,585,520 Van Ess Feb. 12, 1952 2,616,906 Asseif Nov. 4, 1952 2,623,016 Mertes Dec. 23, 1952 2,671,758 Vinograd Mar. 9, 1954 

1. A PROCESS FOR THE PREPARATION OF OIL-SOLUBLE LIQUID, FILTERABLE COMPOSITIONS CONTAINING LARGE AMOUNTS OF METAL WHICH COMPRISES: PREPARING AND MIXING A MASS IN WHICH AT 50*C., AT LEAST 50% OF THE MASS IS IN THE LIQUID STATE,, AND IN WHICH MASS THE ACTIVE COMPONENTS CONSIST ESSENTIALLY OF A LEAST ONE EACH OF ONE EACH OF THE FOLLOWING COMPONENTS: (A) A SUBSTANTIALLY NEUTRAL, ALPHATIC KETONE HAVING AT LEAST 13 CARBON ATOMS AND A VAPOR PRESSURE LESS THAN ATMOSPHERIC AT 225* C., (B) A MONOHYDRIC ALCOHOL CONTAINING NO HOMOCYCLIC BENZENOID RING AND HAVING A MOLECULAR WEIGHT LESS THAN 150; (C) A LBASICALLY REACTING INORGANIC METAL COMPOUND HAVING A PH GREATER THAN 7 IN AQUEOUS SOLUTIONS AT 25*C. IN AN AMOUNT EQUAL TO AT LEAST 1.5 TIMES THE AMOUNT OF (A) ON AN EQUIVALENCE BASIS; HEATING THE MASS TO A TEMPERATURE OF FROM ABOUT 250* C. TO ABOUT 350* C FOR A PERIOD OF AT LEAST ABOUT 1 HOUR. 